New models of interstellar gas–grain chemistry – I. Surface diffusion rates

In recent years it has become evident that large differences can exist between model results of grain-surface chemistry obtained from a rate equation approach and from a Monte Carlo technique. This dichotomy has led to the development of a modified rate equation method, in which a key element is the artificial slowing down of the diffusion rate of surface hydrogen atoms. Recent laboratory research into the surface diffusion rate of atomic hydrogen suggests that atomic hydrogen moves more slowly on grains than heretofore assumed. This research appears to lessen the need for modifications to the rate equation method. Based on the new laboratory work, we have developed appropriate models of gas-phase and grain-surface chemistry in quiescent dense cloud cores to examine the chemical effects of slowing down the rate at which atomic H can scan over dust surfaces. Furthermore, we have investigated the effect of slowing down the rate at which all species can move over grain surfaces.     

New models of interstellar gas–grain chemistry – III. Solid CO2

Solid CO₂ is observed to be an abundant interstellar ice component towards both quiescent clouds and active star-forming regions. Our recent models of gas–grain chemistry, appropriate for quiescent regions, severely underproduce solid CO₂ at the single assumed gas density and temperature. In this paper, we investigate the sensitivity of our model results to changes in these parameters. In addition, we examine how the nature of the grain surface affects the results and also consider the role of the key surface reaction between O and CO. We conclude that the observed high abundance of solid CO₂ can be reproduced at reasonable temperatures and densities by models with diffusive surface chemistry, provided that the diffusion of heavy species such as O occurs efficiently.     

New models of interstellar gas–grain chemistry – II. Surface photochemistry in quiescent cores

The photodissociation of surface species, caused by photons from the cosmic-ray-induced and background interstellar radiation fields, is incorporated into our combined gas-phase and grain-surface chemical models of quiescent dense interstellar cores. For the cores studied here, only cosmic-ray-induced photons are important. We find that photodissociation alters gas-phase and surface abundances mainly at large cloud ages (≳ 10^6–7 yr). The abundances of those surface species, such as H₂O, that are readily reproduced on the surface following photodissociation are not strongly affected at any time. The abundances of surface species that are, on the other hand, reformed slowly via surface reactions possessing activation energy (e.g. CH₃OH) are reduced, while the abundances of associated surface photoproducts (e.g. CO) increase. In the gas phase, inclusion of surface photodissociation tends to increase molecular abundances at late times, slightly improving the agreement with observation for TMC-1.     

Helical fields and filamentary molecular clouds – I

We study the equilibrium of pressure truncated, filamentary molecular clouds that are threaded by rather general helical magnetic fields. We first apply the virial theorem to filamentary molecular clouds, including the effects of non-thermal motions and the turbulent pressure of the surrounding ISM. When compared with the data, we find that many filamentary clouds have a mass per unit length that is significantly reduced by the effects of external pressure, and that toroidal fields play a significant role in squeezing such clouds.
We also develop exact numerical MHD models of filamentary molecular clouds with more general helical field configurations than have previously been considered. We examine the effects of the equation of state by comparing 'isothermal' filaments, with constant total (thermal plus turbulent) velocity dispersion, with equilibria constructed using a logatropic equation of state.
Our theoretical models involve three parameters: two to describe the mass loading of the toroidal and poloidal fields, and a third that describes the radial concentration of the filament. We thoroughly explore our parameter space to determine which choices of parameters result in models that agree with the available observational constraints. We find that both equations of state result in equilibria that agree with the observational results. Moreover, we find that models with helical fields have more realistic density profiles than either unmagnetized models or those with purely poloidal fields; we find that most isothermal models have density distributions that fall off as r ^−1.8 to r ⁻², while logatropes have density profiles that range from r ⁻¹ to r ^−1.8. We find that purely poloidal fields produce filaments with steep radial density gradients that are not allowed by the observations.     

On the detection of interstellar homonuclear diatomic molecules

The pure rotational spectrum of homonuclear diatomic molecules in the interstellar medium is strongly forbidden, and no such spectrum has been detected. In regions of high excitation, vibrational emission may occur, as is widely detected in the case of H₂ in interstellar shocks and photon-dominated regions. However, it is of considerable interest to know the abundance of homonuclear diatomics in quiescent regions. We propose that vibrational emission from homonuclear diatomic molecules in cold clouds may be detectable, where the excitation is mainly through collisions with non-thermal electrons arising from the cosmic-ray ionization of H₂. As an example, we estimate the intensity of emission from N₂ in cold, dark interstellar clouds. We show that such emission is at the limit of detectability with current technology. Other excitation mechanisms may also contribute and enhance this emission.     

H3+ in diffuse interstellar gas

A model is constructed of the material in front of the star Cygnus OB2 no. 12 in which dense cores are embedded in diffuse clumps of gas. The model reproduces the measured abundances of C₂ and CO, and predicts a column density of 910¹⁰ cm² for HCO⁺.     

Desorption processes and the deuterium fractionation in molecular clouds

Several processes have been suggested as ways of returning accreted grain mantles to the gas, thus preventing the total removal of molecules from the gas phase in dark quiescent clouds. We attempt to distinguish between them by considering not only the calculated gas-phase abundances, but also the ratio of the abundances of deuterated species to non-deuterated species. We find that the D/H ratio in molecules is relatively model-independent, but that desorption due to the formation of H₂ on grains gives the best overall agreement with the observations.     

Chemical evolution ahead of Herbig–Haro objects

Compact regions of enhanced HCO⁺ and NH₃ emission have been detected close to a number of Herbig–Haro objects. An interpretation of these detections is the following: a transient clump within the molecular cloud has been irradiated by the shock that generates the Herbig–Haro object. The irradiation releases icy mantles from the grains within the transient clump and initiates a photochemistry. On the basis of this picture, we have developed an extensive chemical model which predicts that a wide range of species, other than NH₃ and HCO⁺, should also be detectable. These include CH₃OH, H₂S, C₃H₄, H₂CO, SO, SO₂, H₂CS and NS. The chemical effects should last ∼  10⁴ yr  .     

Calculations on the rates, mechanisms, and interstellar importance of the reactions between C and NH2 and between N and CH2

The attempt to understand the temperature dependence of the HNC/HCN abundance ratio in interstellar clouds has been long standing and indecisive. In this paper we report quantum chemical and dynamical studies of two neutral–neutral reactions thought to be important in the formation of HNC and HCN, respectively – C+NH₂→HNC+H, and N+CH₂→HCN+H. We find that although these reactions do lead initially to the products suggested by astronomers, there is so much excess energy available in both reactions that the HCN and HNC products are able to undergo efficient isomerization reactions after production. The isomerization leads to near equal production rates of the two isomers, with HNC slightly favoured if there is sufficient rotational excitation. This result has been incorporated into our latest chemical model network of dense interstellar clouds.     

The possibility of nitrogen isotopic fractionation in interstellar clouds

The possibility of nitrogen isotopic fractionation owing to ion–molecule exchange reactions involving the most abundant N-containing species in dense interstellar clouds has been explored. We find that exchange reactions between N atoms and N-containing ions have most influence on the fractionation, although the extent of fractionation is too small to be readily detectable.     

Injection of molecules from the surfaces of grains into the gas phase chemistry of an expanding cloud

We present model results for the chemistry in an expanding cloud or clump in which molecules are injected into the gas phase from grain surfaces when the clump reaches a certain visual extinction A _v during the expansion. We consider separately injection at two different values of A _v, and include a representative large hydrocarbon, C₆H, and sulphur-bearing molecule, H₂SO₄, as well as H₂O and CO. We examine the abundances of certain molecules which have been observed in diffuse and translucent clouds, and compare the results obtained for these abundances with and without an injection during expansion. We also compare our results withpublished observations, and conclude that in most clouds an injection of molecules has occurred.     

Structure and chemistry in the hot molecular core G34.3+0.15

New multifrequency spatial and spectral studies of the hot molecular core associated with the ultracompact HII region G34.3+0.15 have demonstrated an extremely rich chemistry in this archetypal hot core and revealed differing spatial structure between certain species which may be a dynamical effect of chemical evolution. The structure of the hot core has been studied with the JCMT in the high excitation J=19-18 and J=18-17 lines of CH₃CN and with the Nobeyama Millimetre Array at 4 arc resolution in the J=6-5 transition. Comparison with a VLA NH₃(3,3) map shows a displacement between peak emission in the two chemical species which is consistent with chemical processing on a time scale comparable to the dynamical time scale of 10⁵ yrs.A 330-360 GHz spectral survey of the hot core with the JCMT has detected 358 spectral lines from at least 46 distinct chemical species, including many typical of shocked chemistry while other species indicate abundances that reflect the chemistry of a previous cold phase. The first unambiguous detection of ethanol in hot gas has been made. Observations of 14 rotational transitions of this molecule yield a temperature of 125 K and column density 2×10¹⁵ cm^–2. This large abundance cannot be made by purely gas-phase processes and it is concluded that ethanol must have formed by grain surface chemistry.     

Collapse and fragmentation of rotating magnetized clouds – I. Magnetic flux–spin relation

We discuss the evolution of the magnetic flux density and angular velocity in a molecular cloud core, on the basis of three-dimensional numerical simulations, in which a rotating magnetized cloud fragments and collapses to form a very dense optically thick core of  >5 × 10¹⁰ cm⁻³  . As the density increases towards the formation of the optically thick core, the magnetic flux density and angular velocity converge towards a single relationship between the two quantities. If the core is magnetically dominated its magnetic flux density approaches  1.5( n /5 × 10¹⁰ cm⁻³)^1/2 mG  , while if the core is rotationally dominated the angular velocity approaches  2.57 × 10⁻³ ( n /5 × 10¹⁰ cm⁻³)^1/2 yr⁻¹  , where n is the density of the gas. We also find that the ratio of the angular velocity to the magnetic flux density remains nearly constant until the density exceeds  5 × 10¹⁰ cm⁻³  . Fragmentation of the very dense core and emergence of outflows from fragments will be shown in the subsequent paper.     

The formation of heavy hydrocarbons in molecular clouds

Laboratory data on the conversion of solid methane into large hydrocarbons by particle radiation are used to estimate the fraction of interstellar carbon converted by this process into refractory form. We find that the maximum fraction of carbon that can be converted into refractory form during the life of a dense core within an interstellar cloud is in the range of 1–5 per cent. The implication of this result is that the conversion of enough carbon into refractory form to contribute significantly to interstellar extinction requires the frequent passage of material into and out of dense cores. If so, then interstellar clouds must exist for at least 10 Myr. However, these conclusions should be regarded as preliminary until confirmed by further laboratory studies of the particle irradiation of complex ice mixtures.